CN102875830B - Preparation method and application of sulfhydryl chitosan/activated carbon composite functional membrane - Google Patents
Preparation method and application of sulfhydryl chitosan/activated carbon composite functional membrane Download PDFInfo
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- CN102875830B CN102875830B CN201210419031.1A CN201210419031A CN102875830B CN 102875830 B CN102875830 B CN 102875830B CN 201210419031 A CN201210419031 A CN 201210419031A CN 102875830 B CN102875830 B CN 102875830B
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Abstract
The invention relates to a preparation method and application of a sulfhydryl chitosan/activated carbon composite functional membrane, belonging to the technical fields of novel functional membrane material preparation and arsenic-polluted water treatment. The preparation method comprises the following steps: compounding chitosan and activated carbon into a membrane, adding epoxy chloropropane to carry out cross-linking to obtain a cross-linked chitosan/activated carbon composite membrane, modifying the cross-linked chitosan/activated carbon composite membrane with 2,3-dimercaptosuccinic acid, and introducing sulfhydryl group onto the chitosan framework, thereby obtaining the functional membrane. The novel functional membrane prepared by the method provided by the invention can display multiple synergic functions of chitosan, activated carbon and sulfhydryl group, is used for treating arsenic-polluted water, is applicable to wide pH range, does not need the step of preoxidation, can effectively remove As (III) and As (V), is free from the influence of coexistent competitive anions, has the advantages of favorable mechanical strength and simple treatment technique, can be used repeatedly, can greatly lower the cost, and is a new material and method having industrial application prospects.
Description
Technical field
Preparation method and the application of a kind of thio chitosan/gac composite function film, the invention belongs to Functional ized Monolayer Material preparation and water-treatment technology field, and the preparation method who is specifically related to thio chitosan/gac composite function film reaches for the treatment of arsenic polluted water.
Background technology
It is the problem of a global concern that arsenic in water pollutes.The reason that causes arsenic to pollute is mainly due to the use containing arsenic agricultural chemicals and medicament, as weedicide and wood preservative etc.In addition, in the recovery process of arsenic-containing ores, owing to oozing drop, make arsenic enter earth's surface and underground water source, and then cause the arsenic at water source to pollute.Arsenic is a kind of height carcinogens, by the Center for Disease Control and the international mechanism that gives protection against cancer, is defined as I class carcinogens.The tap water arsenic standard of the World Health Organization is 10 μ gL
-1, along with the development of arsenic detection technique, also have the trend further reduced.
In polluted water, the general method adopted of the removal of arsenic has: precipitation (Xu Y, Dai Y, Zhou J
, et al.2010; Janin A, Zaviska F, Drogui P
, et al.2009; Jia Y, Xu L, Fang Z
, et al.2006), absorption (Chai Duoli. 2010,2011; Opiso E, Sato T, Yoneda T. 2009; Mamindy-Pajany Y, Hurel C, Marmier N
, et al.2011; Maji SK, Kao YH, Liu CW. 2011), ion-exchange (An B, Liang Q, Zhao D. 2011; Clifford DA. 1999; Greenleaf JE, Lin J, Sengupta AK. 2006) and flocculation-micro-filtration (de Lourdes Ballinas M, de San Miguel ER, de Jes ú s Rodr í guez MT
, et al.2004; Nguyen VT, Vigneswaran S, Ngo HH
, et al.2009; Kim K, Cho J. 2006; Fogarassy E, Galambos I, Bekassy-Molnar E
, et al.2009; Heimann AC, Jakobsen R. 2007).The main existence form of arsenic in water is H
3asO
3and H
3asO
4and corresponding negatively charged ion.Because As (III) hazardness is larger, and consider that As (V) is easy to remove than As (III), so, in the processing arsenic pollution method that document is mentioned, a pre-oxidation treatment process is arranged usually, after with oxygenant, As (III) being oxidized to As (V), processed (Chai Duoli. 2010,2011).In addition, prior art needs specific pH condition, and can not there is too much competition anion to exist, just treatment effect preferably can be arranged, therefore process comprise preoxidation, the pH regulator before processing and process after pH readjustment step, this must make complex disposal process, processing cost raise, and while in water source, containing various competition anion, treatment effect is very undesirable.Therefore, be badly in need of green, the efficient novel material of development and novel method and process arsenic polluted water.
Summary of the invention
The objective of the invention is the defect existed for solving prior art, preparation method and the application of a kind of thio chitosan/gac composite function film are provided, to realize green, to process arsenic polluted water efficiently.
Technical scheme of the present invention: preparation method and the application of a kind of thio chitosan/gac composite function film can be achieved through the following technical solutions:
The preparation method of a kind of thio chitosan/gac composite function film, comprise the steps:
(1) preparation of chitosan/active carbon composite membrane (CS/C): chitosan (CS) is joined to 0.50molL
-1aqueous acetic acid in, stirring and dissolving, the mass ratio of chitosan and aqueous acetic acid is 1:24～49, obtains chitosan-acetic acid solution; Get powdered active carbon, process with 10% aqueous nitric acid, heated and stirred 2～3 h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; To the dry activated carbon added in chitosan-acetic acid solution after processing, the mass ratio of gac and chitosan is 0.1～0.3:1, stirs, and obtains film-casting liquid; Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane (CS/C);
(2) 0.05 molL of the preparation of cross-linked chitosan/active carbon composite membrane (CS/CL): 50mL
-1the NaOH aqueous solution provides weakly alkaline environment for crosslinking reaction, under 40 ℃, 2～5g CS/C film is immersed, and drips wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane (CS/CL);
(3) preparation of thio chitosan/gac composite function film (CS-SH/C): in reaction vessel, add successively 2,3-dimercaptosuccinic acid 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 60～80g CS/CL film, fully submergence wherein, 38 ℃～40 ℃ reactions of constant temperature, jolting 24h, take out, repeatedly be washed till neutrality with deionized water and ethanol, 35 ℃ of vacuum-dryings, obtain thio chitosan/gac composite function film (CS-SH/C).
The application of the thio chitosan of preparation/gac composite function film, for the treatment of arsenic polluted water, comprise the steps:
Get respectively 0.5 mgmL of 50mL
-1as (III) and As (V) solution, respectively add 40～80mg CS-SH/C functional membrane, and the 8h that vibrates under room temperature measures the concentration of residual ion in sample solution, calculates clearance.
The invention has the beneficial effects as follows: compared with prior art, thio chitosan of the present invention/gac composite function film is not obvious with the variation of pH to the removal ability of arsenic, available in wide pH scope; Without pre-oxidation step, to As (III) and As (V), all can effectively remove, and the impact of the competition anion that do not coexisted; Physical strength is good, can reuse, and treatment process is simple, can greatly reduce costs, and is a kind of novel material and novel method that prospects for commercial application is arranged.Preparation method of this thio chitosan/gac composite function film and products thereof belongs to initiative work with application.
The accompanying drawing explanation
The FT-IR spectrogram that Fig. 1 is embodiment 1 gained functional membrane and raw materials of chitosan in the present invention, wherein 1 is raw materials of chitosan, 2 is the gained functional membrane.
The XRD figure that Fig. 2 is embodiment 1 gained functional membrane and raw materials of chitosan in the present invention, wherein 1 is raw materials of chitosan, 2 is the gained functional membrane.
The arsenic removal rate that Fig. 3 is embodiment 3 gained functional membranes in the present invention and pH graph of a relation, wherein 1 is As (III), 2 is As (V).
The arsenic removal rate that Fig. 4 is embodiment 2 gained functional membranes in the present invention and pH graph of a relation, wherein 1 is As (III), 2 is As (V).
The arsenic removal rate that Fig. 5 is embodiment 3 gained functional membranes in the present invention and reprocessing cycle number of times graph of a relation, wherein 1 is As (III), 2 is As (V).
Embodiment
Below in conjunction with embodiment, the invention will be further described, but application of the present invention is not limited to this.
The present embodiment is the preparation of thio chitosan/gac composite function film (CS-SH/C).Detailed process is: the 0.50molL that 10g chitosan (CS) is joined to 240g
-1in aqueous acetic acid, stirring and dissolving, obtain chitosan-acetic acid solution; Get powdered active carbon, process with the aqueous nitric acid of 10 %, heated and stirred 2h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; Add the dry activated carbon after 1g processes in chitosan-acetic acid solution, stir, obtain film-casting liquid; Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane (CS/C); Get 0.05 molL of 50mL
-1the NaOH aqueous solution provides weakly alkaline environment for crosslinking reaction, under 40 ℃, 2g CS/C film is immersed, and drips wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane (CS/CL); In reaction vessel, add successively DMSA 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 60g CS/CL film, fully submergence wherein, 38 ℃ of reactions of constant temperature, jolting 24h, take out, deionized water and ethanol are washed till neutrality repeatedly, and 35 ℃ of vacuum-dryings obtain thio chitosan/gac composite function film (CS-SH/C).The FT-IR infrared spectra of gained functional membrane (2) and raw materials of chitosan (1) is shown in Fig. 1, and XRD is shown in Fig. 2.The organic element analysis result of gained functional membrane and raw materials of chitosan is: raw materials of chitosan (C%, 42.02%; H%, 6.51%; N%, 8.00%; S%, 0.50%), functional membrane (C%, 49.18%; H%, 4.95%; N%, 5.83%; S%, 9.23%), by the known functional membrane of result, having introduced sulfydryl.
The present embodiment is the preparation of thio chitosan/gac composite function film (CS-SH/C).Detailed process is: the 0.50molL that 10g chitosan (CS) is joined to 300g
-1aqueous acetic acid in, stirring and dissolving, obtain chitosan-acetic acid solution; Get powdered active carbon, by the nitric acid treatment of 10 %, heated and stirred 3h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; Add the dry activated carbon after 2g processes in chitosan-acetic acid solution, stir, obtain film-casting liquid.Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane (CS/C); 0.05 molL of 50mL
-1the NaOH aqueous solution provides weakly alkaline environment for crosslinking reaction, under 40 ℃, 3g CS/C film is immersed, and drips wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane (CS/CL); In reaction vessel, add successively DMSA 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 70g CS/CL film, fully submergence wherein, 39 ℃ of reactions of constant temperature, jolting 24h, take out, deionized water and ethanol are washed till neutrality repeatedly, and 35 ℃ of vacuum-dryings obtain thio chitosan/gac composite function film (CS-SH/C).The organic element analysis result of gained functional membrane and raw materials of chitosan is: raw materials of chitosan (C%, 42.02%; H%, 6.51%; N%, 8.00%; S%, 0.50%), functional membrane (C%, 57.77%; H%, 5.38%; N%, 6.42%; S%, 9.19%), by the known functional membrane of result, having introduced sulfydryl.
The present embodiment is the preparation of thio chitosan/gac composite function film (CS-SH/C).Detailed process is: the 0.50molL that 10g chitosan (CS) is joined to 400g
-1aqueous acetic acid in, stirring and dissolving, obtain chitosan-acetic acid solution; Get powdered active carbon, process with the aqueous nitric acid of 10 %, heated and stirred 3h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; Add the dry activated carbon after 2g processes in chitosan-acetic acid solution, stir, obtain film-casting liquid.Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane (CS/C); 0.05 molL of 50mL
-1the NaOH aqueous solution provide weakly alkaline environment for crosslinking reaction, under 40 ℃, 4g CS/C film is immersed, drip wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane (CS/CL); In reaction vessel, add successively DMSA 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 80g CS/CL film, fully submergence wherein, 40 ℃ of reactions of constant temperature, jolting 24h, take out, deionized water and ethanol are washed till neutrality repeatedly, and 35 ℃ of vacuum-dryings obtain thio chitosan/gac composite function film (CS-SH/C).The organic element analysis result of gained functional membrane and raw materials of chitosan is: raw materials of chitosan (C%, 42.02%; H%, 6.51%; N%, 8.00%; S%, 0.50%), functional membrane (C%, 58.87%; H%, 5.42%; N%, 6.23%; S%, 8.12%), by the known functional membrane of result, having introduced sulfydryl.
The present embodiment is the preparation of thio chitosan/gac composite function film (CS-SH/C).Detailed process is: the 0.50molL that 10g chitosan (CS) is joined to 490g
-1aqueous acetic acid in, stirring and dissolving, obtain chitosan-acetic acid solution; Get powdered active carbon, process with the aqueous nitric acid of 10 %, heated and stirred 2h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; Add the dry activated carbon after 3g processes in chitosan-acetic acid solution, stir, obtain film-casting liquid.Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane (CS/C); 0.05 molL of 50mL
-1the NaOH aqueous solution provide weakly alkaline environment for crosslinking reaction, under 40 ℃, 5g CS/C film is immersed, drip wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane (CS/CL); In reaction vessel, add successively DMSA 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 70g CS/CL film, fully submergence wherein, 38 ℃ of reactions of constant temperature, jolting 24h, take out, deionized water and ethanol are washed till neutrality repeatedly, and 35 ℃ of vacuum-dryings obtain thio chitosan/gac composite function film (CS-SH/C).The organic element analysis result of gained functional membrane and raw materials of chitosan is: raw materials of chitosan (C%, 42.02%; H%, 6.51%; N%, 8.00%; S%, 0.50%), functional membrane (C%, 68.25%; H%, 2.21%; N%, 3.02%; S%, 6.12%), by the known functional membrane of result, having introduced sulfydryl.
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), high spot reviews pH removes the impact of arsenic ability on functional membrane, and detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution are adjusted to pH 2～9 with rare nitric acid and sodium hydroxide in small beaker, add 60mg embodiment 3 gained CS-SH/C functional membranes, 8h vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, the results are shown in Figure 3.As shown in Figure 3, arsenic removal rate is subject to the impact of pH value of solution little, and in pH 2～9 scopes, clearance is all more than 90%, and wherein best pH scope is 6～8, is particularly useful for the processing of Arsenic in Drinking Water.
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), high spot reviews pH removes the impact of arsenic ability on functional membrane, and detailed process is: divide 0.5 mgmL that gets 50mL
-1as (III) and As (V) solution are adjusted to pH 2～9 with hydrochloric acid and sodium hydroxide in small beaker, add 60mg embodiment 2 gained CS-SH/C functional membranes, 8h vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, the results are shown in Figure 4.As shown in Figure 4, arsenic removal rate is subject to the impact of pH value of solution little, and in pH 2～9 scopes, clearance is all more than 93%, and wherein best pH scope is 6～8, is particularly useful for the processing of Arsenic in Drinking Water.
Table 1
| Interfering ion | Noiseless ion | HCO 3 - | Cl - | PO 4 3- |
| Interfering ion add-on/As(mass ratio) | 0/1 | 60/1 | 10/1 | 10/1 |
| As (III) clearance | 85.8 | 85.3 | 85.7 | 85.6 |
| As (V) clearance | 76.1 | 73.0 | 74.9 | 74.8 |
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), the high spot reviews competition anion is removed the impact of arsenic ability on functional membrane, and detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution, pH is 7, adds a certain amount of interference anion salt, add 40mg embodiment 1 gained CS-SH/C functional membrane, the 8h that vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, design parameter and the results are shown in Table 1.As shown in Table 1, disturbing the HCO that negatively charged ion is 60 times
3 -, the Cl of 10 times
-pO with 10 times
4 3-substantially do not disturb the clearance of arsenic while existing, show that the CS-SH/C functional membrane is good to the avidity of arsenic, immunity from interference is strong, is applicable to the water sample processing that a large amount of interference negatively charged ion exist.
Table 2
| Interfering ion | Noiseless ion | HCO 3 - | Cl - | PO 4 3- |
| Interfering ion add-on/As(mass ratio) | 0/1 | 60/1 | 10/1 | 10/1 |
| As (III) clearance | 90.0 | 89.7 | 89.6 | 89.2 |
| As (V) clearance | 80.0 | 77.2 | 78.5 | 78.9 |
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), the high spot reviews competition anion is removed the impact of arsenic ability on functional membrane, and detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution, pH is 7, adds a certain amount of interference anion salt, add 40mg embodiment 2 gained CS-SH/C functional membranes, the 8h that vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, design parameter and the results are shown in Table 2.As shown in Table 2, disturbing the HCO that negatively charged ion is 60 times
3 -, the Cl of 10 times
-pO with 10 times
4 3-substantially do not disturb the clearance of arsenic while existing, show that the CS-SH/C functional membrane is good to the avidity of arsenic, immunity from interference is strong, is applicable to the water sample processing that a large amount of interference negatively charged ion exist.
Table 3
| Interfering ion | Noiseless ion | HCO 3 - | Cl - | PO 4 3- |
| Interfering ion add-on/As(mass ratio) | 0/1 | 60/1 | 10/1 | 10/1 |
| As (III) clearance | 86.0 | 85.5 | 85.9 | 85.8 |
| As (V) clearance | 76.0 | 73.2 | 75.4 | 74.6 |
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), the high spot reviews competition anion is removed the impact of arsenic ability on functional membrane, and detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution, pH is 7, adds a certain amount of interference anion salt, add 40mg embodiment 3 gained CS-SH/C functional membranes, the 8h that vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, design parameter and the results are shown in Table 3.As shown in Table 3, disturbing the HCO that negatively charged ion is 60 times
3 -, the Cl of 10 times
-pO with 10 times
4 3-substantially do not disturb the clearance of arsenic while existing, show that the CS-SH/C functional membrane is good to the avidity of arsenic, immunity from interference is strong, is applicable to the water sample processing that a large amount of interference negatively charged ion exist.
Table 4
| Interfering ion | Noiseless ion | HCO 3 - | Cl - | PO 4 3- |
| Interfering ion add-on/As(mass ratio) | 0/1 | 60/1 | 10/1 | 10/1 |
| As (III) clearance | 83.1 | 82.6 | 82.7 | 82.9 |
| As (V) clearance | 73.2 | 70.1 | 72.3 | 71.7 |
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), the high spot reviews competition anion is removed the impact of arsenic ability on functional membrane, and detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution, pH is 7, adds a certain amount of interference anion salt, add 40mg embodiment 4 gained CS-SH/C functional membranes, the 8h that vibrates under room temperature, measure the concentration of residual ion in sample solution, calculate the As clearance, design parameter and the results are shown in Table 4.As shown in Table 4, disturbing the HCO that negatively charged ion is 60 times
3 -, the Cl of 10 times
-pO with 10 times
4 3-substantially do not disturb the clearance of arsenic while existing, show that the CS-SH/C functional membrane is good to the avidity of arsenic, immunity from interference is strong, is applicable to the water sample processing that a large amount of interference negatively charged ion exist.
Embodiment 11
The application of the thio chitosan that the present embodiment is preparation/gac composite function film (CS-SH/C), the regeneration of this functional membrane of high spot reviews and repeat performance, detailed process is: 0.5 mgmL that gets respectively 50mL
-1as (III) and As (V) solution, pH is 7, adds 40mg embodiment 3 gained CS-SH/C functional membranes, 8h vibrates under room temperature; Have the CS-SH/C functional membrane of arsenic to immerse in saturated sodium sulfide solution absorption, mild stirring 2h, remove the arsenic of absorption, and deionized water wash makes film regeneration, and the film after regeneration is reused, and the results are shown in Figure 5.As shown in Figure 5, after 10 reprocessing cycle are used, the performance variation of film is little, therefore, can determine the stable in properties of film, and physical strength is good, by reprocessing cycle, uses, and can greatly reduce costs, and regenerative process is simple.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (3)
1. the preparation method of thio chitosan/gac composite function film, is characterized in that, comprises the steps:
(1) preparation of chitosan/active carbon composite membrane CS/C: chitosan CS is joined to 0.50molL
-1aqueous acetic acid in, stirring and dissolving, the mass ratio of chitosan and aqueous acetic acid is 1:24～49, obtains chitosan-acetic acid solution; Get powdered active carbon, process with 10% aqueous nitric acid, heated and stirred 2～3 h in boiling water bath, filter, and with deionized water, is washed till neutrality, and dry 5 h under 120 ℃, obtain dry activated carbon; To the dry activated carbon added in chitosan-acetic acid solution after processing, the mass ratio of gac and chitosan is 0.1～0.3:1, stirs, and obtains film-casting liquid; Get film-casting liquid 6mL and join in the circular polypropylene molds that diameter is 5cm, 60 ℃ of constant temperature, when volatile weight loss 50% left and right, be immersed in 1molL by film
-1the NaOH aqueous coagulation bath in, solidify 24h in precipitation bath after, with the distilled water flushing film, to neutral, obtain chitosan/active carbon composite membrane CS/C;
(2) 0.05 molL of the preparation of cross-linked chitosan/active carbon composite membrane CS/CL: 50mL
-1naOH solution provide weakly alkaline environment for crosslinking reaction, under 40 ℃, 2～5g CS/C film is immersed, drip wherein 0.01 molL
-1epoxy chloropropane solution 50mL, as linking agent, stirs, and reaction 2h, then rinse film to neutral with deionized water, obtains cross-linked chitosan/active carbon composite membrane CS/CL;
(3) preparation of thio chitosan/gac composite function film CS-SH/C: in reaction vessel, add successively DMSA 400mL, diacetyl oxide 240mL, acetic acid 160mL, vitriol oil 0.6mL, fully mix, jolting, be cooled to room temperature, add 60～80g CS/CL film, fully submergence wherein, 38 ℃～40 ℃ reactions of constant temperature, jolting 24h, take out, deionized water and ethanol are washed till neutrality repeatedly, and 35 ℃ of vacuum-dryings obtain thio chitosan/gac composite function film CS-SH/C.
2. the application of the thio chitosan prepared by claim 1 method/gac composite function film, is characterized in that, for arsenic polluted water, processes, and the addition of this functional membrane is 25mg arsenic: 40～80mg functional membrane.
3. the application of thio chitosan according to claim 2/gac composite function film, is characterized in that, described arsenic polluted water is for containing As (III) or As (V) water.
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| CN114940817B (en) * | 2022-06-27 | 2023-11-21 | 烟台辰宇汽车部件有限公司 | Polyurethane for thrust rod and preparation method thereof |
| CN117531484A (en) * | 2024-01-08 | 2024-02-09 | 成都达奇科技股份有限公司 | Active carbon film material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241837A (en) * | 2011-06-08 | 2011-11-16 | 天津大学 | Thiolated-chitosan-based temperature-sensitive in-situ hydrogel as well as preparation method and uses thereof |
| CN102675675A (en) * | 2012-05-18 | 2012-09-19 | 江南大学 | Dithiocarbamic acid (DTC) modified chitosan macromolecule composite membrane and preparation method |
-
2012
- 2012-10-29 CN CN201210419031.1A patent/CN102875830B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241837A (en) * | 2011-06-08 | 2011-11-16 | 天津大学 | Thiolated-chitosan-based temperature-sensitive in-situ hydrogel as well as preparation method and uses thereof |
| CN102675675A (en) * | 2012-05-18 | 2012-09-19 | 江南大学 | Dithiocarbamic acid (DTC) modified chitosan macromolecule composite membrane and preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 喻胜飞等.壳聚糖活性炭共混超滤膜的研制.《水处理技术》.1999,第25卷(第5期),第255-258页. |
| 壳聚糖活性炭共混超滤膜的研制;喻胜飞等;《水处理技术》;19991015;第25卷(第5期);第255-258页 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10106436B2 (en) | 2013-03-16 | 2018-10-23 | Chemica Technologies, Inc. | Selective adsorbent fabric for water purification |
| NL2027894B1 (en) * | 2020-11-13 | 2022-06-30 | Univ Shandong | Chitosan flexible composite membrane material loaded with activated carbon, and preparation method and application thereof |
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